Translation of abstract (English)

The synthesis, characterization and different applications of several lipophilic anions are presented. The term “lipophilic anion” appears to be a paradox. The electric charge separation of salts in cations and anions in solution is best stabilized by a polar, hydrophilic environment. However, lipophilic anions are characterized by a low negative charge, large molecular dimensions and a lipophilic molecular surface. Related weakly-coordinating anions (WCA) usually comprise fluorine substituents, resulting in a more fluorophilic behavior. The most important structural features of WCAs are, on the one hand, multiple C-F fragments in order to electronically conceal and, on the other hand, bulky substituents to sterically conceal nucleophilic sites within the anion. In contrast, the main principles in designing lipophilic anions are the minimization of electrostatic contact with the positive counterion and the maximization of van-der-Waals interactions with nonpolar solvents. This work´s strategy for designing a lipophilic anion avoids expensive and persistent C-F bonds and uses large and inexpensive tert-butylated 2,2’-biphenols for an extended hydrocarbon molecular surface or (2R,3R)- N,N‘-dioctadecyl-2,3-dihydroxybutyldiamides for borate esters. The structural design of the synthesized anions was supported by computer chemical investigations. For instance, force field calculations were used as a drawing board for the further development of lipophilic anions with improved properties. This will be the agenda for further synthetic approaches. The lithium salts of the 3,3´,5,5´-tetra-tert-butylbiphenyl-2,2´-diol based anions, Li(thf)4 altebate 74 and Li(thf)4 bortebate 129, show an unprecedented high solubility in n-pentane [Li(thf)4 altebate 74: 7 g/L, and Li(thf)4 bortebate 129: 40 g/L at room temperature]. These compounds are stable up to temperatures of 200 °C and can be synthesized in a multiple-gram-scale in an efficient and cheap way [e.g.: Li(thf)4 altebate 74 < 0.1 €/g]. Furthermore, the conductivity and stability towards hydrolysis of selected compounds is presented. Another milestone in the field of lipophilic anions was the development of methods for theincorporation of the aforementioned anions into various salts. For this task, the sodium salts of the altebate 1- and the bortebate 2- with a very low content of tetrahydrofuran ligands (compounds 117 and 131) werde shown to give the best results. In this work, several salt metatheses could be performed by elimination of sodium halides.The activated form of the sodium altebate 117 can easily abstract halide anions from every testedcompound, even from an NHC-silver chloride complex. As a result of its high symmetry, altebate 1- and bortebate 2- salts have a high tendency to form diamond-shaped crystals. Thus, in many singlecrystal X-ray structures (see chapter 14.4) the low tendency of the anions to coordinate to the corresponding cations is shown.Superabsorbent polymers for water are widely established, for example as absorbents in diapers. In 2007, the first superabsorbent polymers for less polar solvents were presented by the group of Sada. For a superabsorbent effect, it is mandatory to establish an osmotic pressure between the inside and the outside of the polymer material. Therefore, a solvated ion pair inside the polymer is needed. The THF adduct of lithium altebate 74 is exceptionally soluble in n-pentane. Due to this fact, altebate 1- is predestinated for superabsorbent polymers for non-polar solvents. By employing the altebate anion, it was possible to synthesize cheap superabsorbent polymers on a gram-scale with high swelling degrees for nonpolar solvents. For example, these polymers containing altebate 1- are able to absorb two hundred times their own mass of dichloromethane. An important and distinguishing feature of the synthesized polymers is their ability to efficiently absorb diesel fuels, a characteristic property which is crucial for future applications.In this thesis, the influence of the polymerization method, the concentration of the crosslinker, different incorporated lipophilic salts and several concentrations of monomers were investigated to optimize the swelling degree and to get mechanically stable polymers at the same time. An intensive investigation of swelling procedures resulted in the possibility of decreasing the swelling time dramatically and also showed interesting results regarding the temperature dependence of the swelling procedure.